US9695318B2 - Inorganic/lignin type polymer composite nanoparticles, preparation method therefor and application thereof - Google Patents

Inorganic/lignin type polymer composite nanoparticles, preparation method therefor and application thereof Download PDF

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US9695318B2
US9695318B2 US15/105,345 US201415105345A US9695318B2 US 9695318 B2 US9695318 B2 US 9695318B2 US 201415105345 A US201415105345 A US 201415105345A US 9695318 B2 US9695318 B2 US 9695318B2
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lignin
inorganic
polymer composite
alkaline
composite nanoparticles
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Xueqing Qiu
Dongjie Yang
Wenyuan GUO
Mingsong ZHOU
Jinhao HUANG
Conghua Yi
Yuan Li
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South China University of Technology SCUT
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L97/00—Compositions of lignin-containing materials
    • C08L97/005—Lignin
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
    • C08G83/001—Macromolecular compounds containing organic and inorganic sequences, e.g. organic polymers grafted onto silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
    • C08H6/00—Macromolecular compounds derived from lignin, e.g. tannins, humic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/0033—
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/10—Encapsulated ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L21/00—Compositions of unspecified rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08L9/02—Copolymers with acrylonitrile
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C08K2003/0893—Zinc
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2227—Oxides; Hydroxides of metals of aluminium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2296—Oxides; Hydroxides of metals of zinc
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/265—Calcium, strontium or barium carbonate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/267—Magnesium carbonate

Definitions

  • the present invention relates to composite nanoparticles, especially inorganic/lignin type polymer composite nanoparticles, preparation method therefor and application thereof.
  • the inorganic/polymer composite nanomaterials which refer to the composite materials, are produced by compounding inorganic nanoparticles with organic high polymers (e.g., plastics, rubbers, etc.) as the continuous phase.
  • organic high polymers e.g., plastics, rubbers, etc.
  • the inorganic/polymer composite nanomaterials not only have the advantages of rigidity, dimensional stability and thermal stability of inorganic nanoparticles, but also have the advantages of processability, toughness and dielectric properties of polymers. They can achieve the superiority not possessed by an individual component through synergy among the components and it can prepare a new high polymer composite material, which has broad application foreground in mechanics, optics, electronics, magnetics, biology and other fields.
  • the inorganic nanoparticles are easy to glomerate in a polymer matrix and difficult to disperse, and have poor compatibility with polymers, there is often no real orderly assembly between the inorganic nanoparticles and the polymers. Uniform dispersion of nanoparticles is the foundation of nanostructure, and also an important properties of composite materials.
  • the inorganic nanoparticles are poor in dispersibility and difficult to be interfused, and are easy to produce an inorganic phase aggregate in the composite material, thus they are neither able to be compounded with polymers on a nano scale nor able to better play nanometer effects, limiting their wide application.
  • the high cost of inorganic nanoparticles is also the reason of their applied limitation.
  • the inorganic nanoparticles are first subject to surface chemical modification with organic compounds that are both inexpensive and environmentally friendly, so as to improve their dispersivity and surface polarity to produce inorganic/organic composite nanoparticles, and then the composite nanoparticles are compounded with polymers to produce the composite nanomaterial, the glomeration among the inorganic nanoparticles can be effectively prevented, which will improve their compatibility with the polymers and their application properties.
  • the surface chemical modifiers of the inorganic nanoparticles are mainly fatty alcohols, amines, fatty acids, silicones, etc., most of which come from fossil resources. While lignin, the biomass resource preceded only by cellulose in content in nature, is rarelyapplied in this field.
  • Non-renewable fossil resources are increasingly depleted, and environmental issues of papermaking waste are becoming increasingly prominent, making recovery and utilization of the lignin renewable resource in the papermaking waste particularly important.
  • lignin is the only non-petroleum resource in nature that can provide renewable aryl compounds, accounting for about 20%-30% by weight of the plant body.
  • the lignin within the plant body is usually dissolved out to become a main component of the waste liquid, and therefore recovery and utilization of the industrial lignin is an effective way to manage the pulping and papermaking waste liquid issues.
  • the alkaline lignin moleculesextracted from the papermaking waste liquid, containing phenolic hydroxyl group, carbonyl group, benzene ring, ether bond, carbon-carbon double bond, etc., rich in active hydroxyl groups on the surface, can be endowed with excellent reactivity and adsorption properties through chemical modification, achieve the hydrophilic-lipophilic balance value of different proportions, and therefore be stably dispersed in polymers of different polarity.
  • lignin is renewable, degradable, nonpoisonous, inexpensive and widely available and has other advantages and is an excellent “green” chemical raw material, and therefore its comprehensive utilization draws much attention.
  • the modified alkaline lignin has been widely used as a dispersant in pesticides, ceramics, coal water slurry, cement, dyes and other fields.
  • the alkaline lignin currently still at a low value-added level, how to utilize the widely available industrial lignin to develop a greater variety of lignin products with excellent properties to achieve the high-value utilization of lignin will become an important direction of the lignin research.
  • Efficiently modifying the alkaline lignin to prepare the lignin type nanomaterials will bring novel and wide application foreground for lignin, and also promote the high-value utilization of lignin to a new height.
  • a Chinese patent CN 101173107B disclosed lignin-inorganic nanocomposite materials and preparation method therefor on Mar. 16, 2011, which used the following preparation method: First pretreating the inorganic nanoparticles with lignosulfonic acid, ammonium lignosulfonate and other water-soluble lignin surface treatment agents and coupling agents, then adding them to the lignin or their derivatives, and then carrying out acid precipitation, filtration and drying to obtain the product. Cheng Xiansu et al.
  • lignin/inorganic nanocomposite particles has many disadvantages: (1) In the preparation process, expensive silane coupling agent, titanate coupling agent, zirconate coupling agent, etc., or an organic solvent which contain certain toxicity needs to be used as an assistant for surface modification of inorganic nanoparticles, and the preparation cannot be performed at room temperature and atmospheric pressure, thus increasing the cost; (2) the lignin used, undergoing no necessary chemical modification, cannot achieve dispersibility fundamentally; with weak interaction between lignin and inorganic nanoparticles, the inorganic nanoparticles can be pre-dispersed only after a lignin surface treatment agent is additionally added as a dispersant. Therefore, the prepared composite nanoparticles still suffer from serious surface agglomeration, difficult to have their properties improved significantly in application to high polymer materials.
  • the one purpose of the present invention is as follows: In order to overcome the defects of the inorganic nanoparticles such as easy glomeration in the polymer matrix, difficulty in dispersion, and poor compatibility with polymers, chemically modifying the alkaline lignin by grafting active groups, then using the alkaline lignin to chemically modify the surface of the inorganic nanoparticles, and then using the synergy between the modified alkaline lignin and the inorganic nanoparticles to produce the affordable and uniformly dispersed inorganic/lignin polymer composite nanoparticles with excellent properties, which are then compounded efficiently with plastics, rubbers and other high polymers to improve their mechanical properties.
  • the lignin type polymer using the alkaline lignin as the main raw material, is grafted with a carboxyl group, a phosphate group and other active groups through chemical modification at atmospheric pressure, thereby enhancing the interaction between the lignin type polymer and the inorganic nanoparticles.
  • adsorption of the lignin type polymer on the inorganic nanoparticles together with the steric hindrance formed by the three-dimensional spatial network structure of the lignin itself, glomeration among the inorganic nanoparticles can be overcome effectively to make the inorganic nanoparticles dispersed uniformly.
  • the prepared inorganic/lignin type polymer composite nanoparticles have good dispersibility, and strong compatibility with high polymers.
  • This composite material can significantly improve the mechanical properties of high polymer materials such as plastics and rubbers,
  • Another purpose of the present invention is to provide a method of preparing the above inorganic/lignin type polymer composite nanoparticles.
  • the preparing method of the inorganic/lignin type polymer composite nanoparticles is provided, characterized by comprising the following steps:
  • the alkaline lignin solid was dissolved into water to form suspension at concentration of 30%-50% by weight, adjusting the pH to 9-12 with an alkalinity regulator, heating to 60° C.-90° C., adding an activating agent, and reacting for 0.5-2 hours; dissolving a carboxylating agent in a formulation into water to formulate a solution at a concentration of 10%-30% by weight and adding to the above alkaline lignin suspension, and reacting for 1-3 hours at 60° C.-90° C. to produce the carboxylated alkaline lignin;
  • Step (3) mixing the carboxylated alkaline lignin in Step (1) with the hydroxyl phosphate type compound in Step (2), adjusting the pH to 10-13 with an alkalinity regulator, heating to 75° C.-95° C., reacting for 0.5-2 hours, and cooling to room temperature to produce a liquid lignin type polymer;
  • the activating agent is one or two agents selected from the group consisting of dioxane, sodium periodate, ethanol, isopropanol and acetone;
  • the inorganic nanoparticles are one selected from the group consisting of nano silica, nano alumina, nano zinc oxide, nano titanium dioxide and nano calcium carbonate;
  • the carboxylating agent is one or two agents selected from the group consisting of monochloroacetic acid, monobromoacetic acid, monoiodoacetic acid, sodium monochloroacetate and dichloroacetic acid;
  • the phosphorylating agent is one or two agents selected from the group consisting of sodium dihydrogen phosphate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, potassium dihydrogen phosphate and diammonium hydrogen phosphate; and
  • the pretreatment agent is one selected from the group consisting of ethanol, acetone, glycerol, isopropanol and cyclohexane.
  • the alkaline lignin is one or two substances selected from the group consisting of wheat straw alkaline lignin, bamboo pulp alkaline lignin, reed alkaline lignin, wood pulp alkaline lignin, cotton pulp alkaline lignin and bagasse alkaline lignin.
  • the alkalinity regulator is NaOH aqueous solution at a concentration of 30% by mass.
  • the acidity regulator is sulfuric acid, phosphoric acid or hydrochloric acid.
  • the sulfuric acid, the phosphoric acid or the hydrochloric acid has a mass concentration of 10%-30%.
  • An inorganic/lignin type polymer composite nanoparticle is provided, prepared by the above method.
  • inorganic/lignin type polymer composite nanoparticles Blending the inorganic/lignin type polymer composite nanoparticles and plastics or rubbers in an amount of 10%-40% by dry-basis weight of plastics or rubbers, to produce a high polymer composite material.
  • the lignin type polymer molecule of the present invention contains a carboxyl group, a phosphate group and other active groups, which increase adsorption sites and adsorption strength of the lignin type polymer on the surface of the inorganic nanoparticles and, together with the steric hindrance formed by the three-dimensional spatial network structure of the lignin itself, can effectively overcome glomeration among the inorganic nanoparticles to make the inorganic nanoparticles dispersed uniformly.
  • the prepared inorganic/lignin type polymer composite nanoparticles have good dispersibility and strong compatibility with high polymers, and can remarkably improve the mechanical properties of high polymer materials such as plastics and rubbers, with their amount at 10%-40% by dry-basis weight of the plastics or the rubbers.
  • the raw material used in the present invention is the alkaline lignin recovered from the alkaline pulping waste, belonging to renewable resources. With the preparation process proceeding under normal pressure, the present invention has simple process, excellent cost performance, and high efficiency.
  • FIG. 1 shows the infrared spectrum of the lignin type polymer prepared in Example 5 and the raw material wood pulp alkaline lignin.
  • FIG. 2 shows a TEM image of nano silica.
  • FIG. 3 shows a TEM image of the silica/lignin type polymer composite nanoparticles prepared in Example 1.
  • FIG. 1 shows an infrared spectrum of the lignin type polymer prepared in Example 5 (referred to as “Example 5”) and the raw material wood pulp alkaline lignin. It can be known from this figure that, compared to the wood pulp alkaline lignin, Example 5 has weaker absorption than the alkaline lignin at 2940 cm ⁇ 1 (C—H stretching vibration of a methyl, a methylene and a methine) and 1120 cm ⁇ 1 (C—O on a lilac unit), indicating that the modification reaction removes a methoxyl off part of the aromatic ring;
  • Example 5 has weaker absorption than the alkaline lignin at 1610 cm ⁇ 1 and 1520 cm ⁇ 1 (skeletal vibration of an aromatic ring), 1460 cm ⁇ 1 (deformation of a methyl C—H) and 1230 cm ⁇ 1 (C ⁇ O stretching of a guaiacyl), indicating that the modification reaction changes the molecular structure of the
  • FIG. 2 shows a TEM image of nano silica.
  • FIG. 3 shows a TEM image of the silica/lignin type polymer composite nanoparticles prepared in Example 1. It can be seen obviously by comparing FIG. 2 and FIG. 3 that, nano silica is easy to agglomerate and has poor dispersibility, while the prepared silica/lignin type polymer composite nanoparticles have good dispersibility and significantly reduced glomeration among particles, and also have a uniform particle size of about 35 nm With the process used in other examples similar to Example 1, it is found through tests that the TEM images of the products obtained in other examples are basically consistent with those of the products of Example 1, and will therefore not be repeated.
  • Table 1 shows the results of blending modification of the inorganic/lignin type polymer composite nanoparticles obtained in Examples 1, 3 and 4 of the present invention and the high-density polyethylene.
  • the experimental operation method is as follows: Mixing an assistant (calcium carbonate, nano silica or the products of the examples) with high-density polyethylene pellets according to a certain mass ratio, then physically blending them at 150° C. with a mill for 20 minutes, and then molding the cake to produce the assistant/high-density polyethylene composite material.
  • the tensile strength, tensile elongation at break and other mechanical properties of the composite material are determined with an MTS universal tester, and density as well.
  • the calcium carbonate used in the experiments is the modified calcium carbonate used in the industrial blow molding. It can be seen from Table 1 that, although the tensile elongation at break of each composite material is lower than that of the high-density polyethylene, the tensile elongation at break of the composite materials obtained from Examples 1, 3 and 4 is far greater than that of the composite materials obtained from calcium carbonate or nano silica, which indicates that the composite materials obtained from Examples 1, 3 and 4 have good toughness and have exceeded the calcium carbonate strengthened polyethylene materials currently commonly used in industry.
  • the tensile strength of the composite materials obtained from Examples 1, 3 and 4 is 30.33 Mpa, 29.78 Mpa and 29.96 Mpa, respectively, greater than 24.85 Mpa of the calcium carbonate strengthened polyethylene material, 25.34 Mpa of the nano silica strengthened polyethylene material, and 21.98 Mpa of the high-density polyethylene, which indicates that composite materials obtained from Examples 1, 3 and 4, compared with the original plastics and calcium carbonate or nano silica strengthened plastics, have tensile strength that is not reduced but significantly increased.
  • the data of density indicate that, the composite materials obtained from Examples 1, 3 and 4 are between the original high-density polyethylene and the calcium carbonate or nano silica strengthened polyethylene material in density; compared with the inorganic calcium carbonate or nano silica strengthened polyethylene material, the inorganic/lignin type polymer composite nanoparticles obtained in the present invention have advantage in density; therefore, under the same volume, the composite materials obtained from Examples 1, 3 and 4 have less mass, which characteristic will be advantageous to broadening their application field and reducing cost.
  • Table 2 shows the results of blending modification of the inorganic/lignin type polymer composite nanoparticles obtained from Examples 2 and 6 of the present invention and the acrylonitrile-butadiene rubber.
  • the experimental operation method is as follows: At normal temperature, adding 100 parts of acrylonitrile-butadiene rubber to a two-roller mill, adding in turn 1.5 parts of sulfur, 5 parts of zinc oxide, and 1 part of stearic acid to blend, adding a strengthening agent (nano silica or products of the examples) according to a certain mass ratio (10-40 parts) to blend, and then adding 1 part of an accelerant DM (dibenzothiazole disulfide) to blend for 15 min. Vulcanizing the blending product at 145° C.
  • the lignin molecules can provide an intermolecular hydrogen bond, an electrostatic force, the ⁇ - ⁇ stacking interaction, the cation- ⁇ interaction and other various intermolecular forces, and have active chemical reaction activity and good compatibility with the rubber molecules having polarity; with the synergy between the alkaline lignin and the inorganic nanoparticles, the particles are uniformly dispersed and have high surface activity, making the acting force between the inorganic/lignin type polymer composite nanoparticles and the rubber molecules increased, cohesion of gross rubber increased, and the chain segment not easy to slide while being stretched.
  • the three-dimensional spatial network structure of the lignin is advantageous to increasing its crosslinking density with rubber molecules, thus increasing the tensile strength of the rubber composite materials.
  • the rubber filled with the products from Examples 2 and 6 is superior in peeling strength to the rubber filled with nano silica.
  • the rubbers strengthened with the products from Examples 2 and 6 and with nano silica have less elongation at break than the pre-compounded acrylonitrile-butadiene rubber, because addition of a filler may increase crosslinking density of the rubber in the vulcanizing process, thus reducing elongation at break of the rubber.
  • the rubbers filled with the products from Examples 2 and 6 are both superior to the rubber filled with nano silica, which indicates that the composite materials obtained from Examples 2 and 6 have good toughness, and the rubber is not easy to be destroyed in the deformation process and has exceeded the rubber material strengthened with nano silica that is currently commonly used in industry.
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CN104312181B (zh) * 2014-10-24 2017-02-15 华南理工大学 一种多羟基木质素/二氧化硅复合纳米颗粒及其制备方法
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